Rubberlike butadiene copolymers



Patented June 11, 1941 2,422,371

"UNITED STATES PATENT. OFFICE aunnaamm nu'rlmmun coroLxMERs Frank K. Schoeni'eld, Silver Lake, Ohio, assignor to The B. F. Goodrich Company, New York, N. Y., a corporation of New York No Drawing. Application March 5,1941,

Serial No. 881,877

7 Claims. (Cl. 260-845) l 2 h s nventi relates to e -like O P Y- -contain from 2 to 5 carbon atoms in the alcohol mers and to a method for preparing the same. radical may be copolymerized with butadiene and More particularly it relates to the preparation of that a rubber-like copolymer having the desiruseful rubber-like copolymers by the copolymerable properties sought for may be obtained by ization of a mixture of unsaturated organic com.- 5 the polymerization oi! monomer mixtures conpounds containing a high proportion of a containing only small proportions of the ester. Spejugated diene hydrocarbon such as butadiene. cifically I have discovered that ethyl methacryl- The principal object of the invention is to provide ate, propyl methacrylate, isopropyl methacrylate, new butadiene copolymers, particularly rubberbutyl methacrylate, isobutyl methacrylate or like materials having high elasticity, low perma- 1o amyl methacrylate may be copolymerized with nent set and high tensile strength which are butadiene in proportions as high as molecular especially desirable for use in the production of proportions of butadiene to only 1 molecular proportion of the ester to produce rubber-like coy rubber-like c p lymers prepared by the polymers. having mechanical strength and plaspolymerization of a mixture containing butadil5 ticity equivalent to that of known butadiene coene and some other compound copolymerizable polymers which are prepared using much larger therewith, known as comonomer, have already proportions of the comonomer, and having greatbeen disclosed. For examples, U; S. Patent er rebound, elasticity and lower permanent set 1,973,000 of Konrad and Tschunkur discloses a than such known rubber-like copolymers,

copolymer of butadiene and acrylonitrile, U. S. It is recognized that copolymers of butadiene Patent 1,938,731 of Tschunkur and Bock disand methyl methacrylate are known. It is also closes a copolymer of butadiene and styrene, recognized that polymers of both methyl methac- British Patent 370,822 discloses copolymers of rylate and methacrylic esters having from 2 to 5 butadiene with certain acrylic esters, particularcarbon atoms in the alcohol radical are known. 1y methyl acrylate and butyl acrylate and U. S. Moreover, it is known that polymers of methyl Patent 2.218,362 oi Starkweather and Collins as methacrylate alone are far superior to the polywell as British Patent 485,941 disclose a copolymers of other methacrylic esters. For example, mer of butadiene and methyl methacrylate. Hill in U. S. Patent 1,980,483 states that the pol- However, in all these examples of the production ymers of. methyl methacrylate are far superior of butadiene copolymers as shown by the prior to the polymers of ethyl methacrylate and Rdhm art, it is necessary to employ appreciable proporand Bauer in U. S. Patent 2,193,742 state that the tions of the comonomer, about 25 to 50% by tensile strength and hardness of polymerized weight of the mixture or about one molecular methacrylic esters decrease as the number of proportion oi. the comonomer for two or three of carbon atoms in the alcohol radical is increased. butadiene in order to obtain a useful rubber-like By this invention, I have discovered, however, D ymer. When a smaller proportion of the that the copolymers of butadiene with ethyl comonomer is employed the product resembles methacrylate or with other methacrylic esters polybutadiene and does not possess sufficient having from 2 to 5 carbon atoms in the alcohol strength to be of use as a replacement for natural radical are equ l r v n Superior 0 e c p rubber, while, on the other hand, if the comonymers of butadiene with methyl methacrylate, omer is employed in a larger proportion the and that these copolymers may be prepared with product is resinous and stiff rather than rubbera much smaller proportion of the ester.

like and is not elastic or plastic enough to take As is the case with other copolymeric systems the place of natural rubber. In view 01' this fact the specific properties of the copolymers preand the further fact that the comonomer is much pa ed om butadie e and a yl e hac yl tes more expensive than butadiene, it would be excontaining from 2 to 5 carbon atoms in the alcotremely desirable to discover a compound which hol radical, in accordance with this invention, would yield a rubber-like copolymer having demay-be varied somewhat by varying the relative sirable properties when copolymerized with butap p ns of t tWO components. In eneral,

, diene in proportions materially lower than those rubber-like copolymers are obtained from the necessary with previously known comonomers. copolymerization of mixtures containing from After extensive tests with a large number of about 2 to about 15 molecular proportions of a materials which conceivably might be capable of conjugated butadiene hydrocarbon to one moleccopolymerizing with butadiene, I have discovular proportion of the ester. To secure the best ered that alkyl esters of methacrylic acid which results however and at the same time to efiect a saving in the amount of comonomer it is preferable to employ from about ii to 12 m les of butadiene per mole of the ester.

The copolymerization of the mixture of butadiene with the alkyl methacrylate may be carat out for the most part by standard methods In the emulsion copoiymerization process the mixture of monomers ls emulsified with water with the aid of a suitable emulsifying agent. other substances which favorably influence the polymetlon reaction or which improve the properties of the copolymer such as polymerization initiators, polymerization catalysts, polymerization modifiers and the like are added to the emulsion, and the emulsion is allowed to polymerize by agitating the same continuously at a suitable temperature, usually from 20 to 80 C. for a time suflicient to complete the reaction, about to 100 hours usually being required. The copolymer is thus obtained in the form of an aqueous dispersion resembling natural rubber latex to which an age resister or antioxidant may be added if desired and which may then be utilized as such or coagulated by the same methods used to coagulate natural rubber latex for example by addition of acid, alcohol or salts orby a combination of these methods. The copolymerization products are washed and dried to produce a crude rubber-like material which may be processed, compounded, and vulcanized in substantially the same manner as natural rubber.

The following examples will illustrate the process but are not intended to limit the scope of the invention.

Example 1 One hundred parts by weight of a monomermixture containing butadiene and ethyl methacrylate in the ratio of five molecular proportions of butadiene to one of ethyl methacrylate are emulsifled with 250 parts of a 2% aqueous solution of myristic acid which has been 85% neutralized with caustic soda. Ten parts of a 3 /2% aqueous solution of hydrogen peroxide are added as an initiator of polymerization, 1 part of the complex salt sodium ferri pyrophosphate is added to accelerate the polymerization and 0.3 part of diisopropyl dixanthogen disulfide is added as a polymerization modifier. The emulsion is allower to copolymerize by agitation for 21 hours at a temperature of 40 0. Two parts of phenylbeta-naphthylamine are added to the latex-like dispersion resulting from the polymerization and the dispersion is coagulated with a mixture of alcohol and salt. A 95% yield of a plastic, elastic rubber-like material is obtained. The material may be masticated without dimculty on either .a hot or cold mill and may otherwise be processed in the same manner as natural rubber. When the material is compounded in a typical tire tread recipe and then vulcanized it yields an excellent vulcanizate having a tensile strength of 4100 lbs. per sq. in. and an ultimate elongation of 640%. The cured stock also has a low permanent set, high rebound elasticity and is somewhat resistant to swelling by solvents, the swelling in acetone being unusually low. Automobile tires which are the equivalent of tires made of natural rubber and which in some respects are even superior to tires made of natural rubber may be made from this material.

1 at a temperature of 40 0.

Example I! Qne hundred parts by weight of a monomer mixture containing ten molecular proportions of butadiene to one of butyl methacrylate are emulallied with 250 parts of a 3% solution of sodium ate: .15 part of hydrogen mroxide, .50 part of sodium ferri pyrophosphate and .45 part of a mlymerization modifier are added, and the emulsion is allowed to copolymerize for 40 hours Upon coagulation of the latex resulting from the copolymerization a strong elastic rubber-like product is obtained. when compounded and vulcanized this product gives a vulcanizate which is equal in tensile strength to a similar vulcanizate of a copolymer prepared from a mixture of butadiene and methyl methacrylate in which the monomer ratio was three moles of butadiene for one mole of methyl methacrylate.

It is to be understood that other emulsifying agents, initiators. accelerators and modifiers may be substituted inthe above examples with equally good results. As emulsifying agents a number of substances which are capable of forming a stable emulsion of the monomers in water may be employed. Ordinary soaps such as the sodium or potassium salts of saturated or unsaturated fatty acids or mixtures of these, for example. sodium myristate, sodium palmltate, sodium oleate 'and the like, either completely neutralized and containing some free fatty acid, or synthetic saponaceous materials such as hymolal sulfates or sulfonates, aromatic sulfonates. and salts of high molecular weight aliphatic bases; for examples. sodium lauryl sulfate, soduim naphthalene sulfonate, diethylaminoethyloleyl amide hydrochloride, cetyl trimethyl ammonium methyl sulfate, cetyl piperidinium methyl sulfate or some other emulsifying agent may be employed. The emulsion, depending upon the emulsifying agent and the particular polymerization initiator and polymerization catalysts employed, may be either alducted over a wide range of pH. Alkaline emulsions, however, are preferred.

As initiators of polymerization and well known Oxygen yielding compounds such as hydrogen peroxide, benzoyl peroxide, potassium persulfate, sodium perborate and the like may be employed as may also other polymerization initiators such as sulfur dioxide, diazoamino benzene and the like. Polymerization catalysts such as carbon tetrachloride or trichloro acetic acid may be present if desired. Other polymerization catalysts in addition to the sodium ferri pyrophosphate, used in the examples above, which are effective in increasing the yield and decreasing,

the time necessary to complete the polymerization, include a large number of so-called redox systems which contain small proportions of a heavy metal in combination with a wide number of organic or inorganic compounds, which combinations are disclosed more fully in copending applications of William D. Stewart, Serial Nos. 379,712, 379,713, 379,714, 379,715, 379,716 and 379,717, filed February 19, 1941. Polymerization modifiers such as dialkyl dixantho'gens, diaryl disulfides, and other organic sulfur containing compounds which increase the plasticity and solubility of the copolymer may also be employed in the emulsion polymerization process of this invention as described in the specific examples. above.

Although the invention has been described with 5 particular reference to butadiene copolymers it is to be understood that other conjugated butadiene hydrocarbons such as isoprene and dimethyl butadiene may be substituted for a part or all of the butadiene. Then too, other comonomers known to the art such as acrylonitrile, styrene and vinylidene chloride may be included in the mixture of butadiene and the alkyl methacrylic esters of this invention before polymerization, if desired.

The products of this invention are useful in the rubber art for practically all purposes for which natural rubber and other known rubber: like materials may be used. Compounding and vulcanizing of the crude rubber-like products to produce vulcanized articles is carried out in the usual manner and will be apparent to those skilled in the art. The copolymers of this invention are particularly useful to the art since smaller proportions of the comonomer are employed in the production of the copolymer than has heretofore been possible while equally good and, in some respects, surprisingly better copolymers are obtained.

Iclaim:

1. A rubber-like copolymer obtained by the copolymerization of a mixture containing from two to about fifteen molecular proportions of a conjugated butadiene hydrocarbon to one molecular proportion of an alkyl ester of methacrylic acid which contains from,two to five carbon atoms in the alkyl radical.

2. A rubber-like copolymer obtained by the emulsion copolymeriaztion of a mixture containin: from two to about fifteen molecular pro-, portions of butadiene to one molecular prop rtion of an alkyl ester of methacrylic acid which contains from two to five carbon atoms in the alkyl radical.

3. A rubber-like copolymer obtained by the emulsion copolymerization of a mixture containing from two to fifteen molecular proportions of butadlene to one molecular proportion 01' butyl metbacrylate.

4. The process which comprises copolymerizing a mixture containing from two to about fifteen molecular proportions of a conjugated butadiene hydrocarbon to one molecular Proportion of an alkyl ester of methacrylic acid which contains from two to five carbon atoms in the alhl radical.

5. The process which comprises copolymerizing in aqueous emulsion a. mixture containing from two to about fifteen molecular proportions of butadiene to one molecular proportion of an alkyl ester of methacrylic acid which contains from two to five carbon atoms in the alkyl radical.

6. The process which comprises copolym'erizing in aqueous emulsion a mixture containing from two to fifteen molecular proportions of butadiene to one molecular proportion of butyl methacrylate.

7. The process which comprises copolymerizing in aqueous emulsion a mixture containing from five to twelve molecular proportions of butadiene to one molecular proportion of butyl methacrylate.

FRANK K. SCHOENFELD.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Great Britain May 25, 1938 

